CN114014834A - Preparation method of difluoroethylene carbonate - Google Patents
Preparation method of difluoroethylene carbonate Download PDFInfo
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- CN114014834A CN114014834A CN202111488815.5A CN202111488815A CN114014834A CN 114014834 A CN114014834 A CN 114014834A CN 202111488815 A CN202111488815 A CN 202111488815A CN 114014834 A CN114014834 A CN 114014834A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
The invention discloses a preparation method of difluoroethylene carbonate, which comprises the following steps: s1: adding a certain amount of solid fluoride into a container at room temperature under the protection of nitrogen, adding a solvent, and stirring and mixing uniformly; s2: dropwise adding ethylene dichlorocarbonate into an S1 mixed system for reaction at a certain temperature, after dropwise adding is finished for 2-6 hours, monitoring the reaction by using a gas chromatography after dropwise adding is finished, and cooling and finishing the reaction when the content of the ethylene dichlorocarbonate is lower than 0.1%; s3: filtering out solid insoluble substances after the reaction of S2 is finished, and carrying out reduced pressure rectification on the mother liquor to obtain a crude product; s4: purifying the difluoroethylene carbonate to electronic grade through continuous crystallization and sweating. The method changes dichloroethylene carbonate into valuable, prepares the electronic grade difluoroethylene carbonate, greatly reduces the generation amount of hazardous wastes, reduces the environmental protection cost, has simple process and low energy consumption, and is suitable for large-scale production and application.
Description
Technical Field
The invention relates to the technical field of lithium ion battery electrolyte additives, in particular to a preparation method of difluoroethylene carbonate.
Background
The difluoro ethylene carbonate has the advantages of high dielectric constant, high flash point, low freezing point, good oxidation resistance stability and the like, can obviously improve the cycle performance, high temperature performance and flame retardant property of the electrolyte, and is an ideal additive for the lithium battery electrolyte.
The chloroethylene carbonate is a common raw material for preparing vinylene carbonate and fluoroethylene carbonate, and chlorine gas and the chloroethylene carbonate are subjected to substitution reaction to prepare the chloroethylene carbonate industrially, and a byproduct of the dichloroethylene carbonate is the dichloroethylene carbonate. The difluoroethylene carbonate is small in dosage at present, but excellent performance of the difluoroethylene carbonate is gradually favored by various manufacturers, the dichloroethylene carbonate has good market prospect, and the preparation of the electronic difluoroethylene carbonate from the dichloroethylene carbonate can greatly improve the yield of products, reduce wastes and realize a green process. At present, the dichloroethylene carbonate does not have an industrialized recycling scheme, the chlorine content of the dichloroethylene carbonate exceeds 45 percent, the waste treatment has higher requirements on equipment, the treatment process is complex, and the cost is high.
Disclosure of Invention
The invention aims to provide a preparation method of difluoroethylene carbonate, which aims to solve the problems that the chlorine content of dichloroethylene carbonate exceeds 45%, the requirement on equipment for waste treatment is high, the treatment process is complex and the cost is high in the prior art which proposes a recycling scheme that the dichloroethylene carbonate is not industrialized.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of difluoroethylene carbonate comprises the following steps:
s1: adding a certain amount of solid fluoride into a container at room temperature under the protection of nitrogen, adding a solvent, and stirring and mixing uniformly;
s2: dropwise adding ethylene dichlorocarbonate into an S1 mixed system for reaction at a certain temperature, after dropwise adding is finished for 2-6 hours, monitoring the reaction by using a gas chromatography after dropwise adding is finished, and cooling and finishing the reaction when the content of the ethylene dichlorocarbonate is lower than 0.1%;
s3: filtering out solid insoluble substances after the reaction of S2 is finished, and carrying out reduced pressure rectification on the mother liquor to obtain a crude product;
s4: purifying the difluoroethylene carbonate to electronic grade through continuous crystallization and sweating;
s5: recovering the solvent during the rectification of S3;
preferably, the solvent in step S1 includes, but is not limited to, one or more of ethyl acetate, methyl acetate, ethyl propionate, γ -butyrolactone, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate, and most preferably, dimethyl carbonate is used.
Preferably, the solvent in step S1 is a mixture of
And (4) solvent after molecular sieve dehydration.
Preferably, in step S1, the fluoride is one or more of sodium fluoride, potassium fluoride, triethylamine trihydrofluoride and fluorinated quaternary ammonium salt, and most preferably, potassium fluoride is used.
Preferably, the reaction temperature in the step S2 is 50-100 ℃.
Preferably, in the step S2, the purity of dichloroethylene carbonate is 80% to 98%, and the equivalent ratio of dichloroethylene carbonate to potassium fluoride is 1:1 to 1: 5.
Preferably, the reaction time after the completion of the dropwise addition in the step S2 is 1 to 2 hours.
Preferably, the operating temperature of the vacuum rectification in the step S3 is 30-110 ℃, and the operating pressure is 20-100 mmHg.
Preferably, in the step S4, the crystallization sweating temperature-reducing speed is maintained at 1-10 ℃/h, and the temperature-increasing speed is maintained at 1-10 ℃/h.
Compared with the prior art, the invention has the beneficial effects that:
the method changes dichloroethylene carbonate into valuable, prepares the electronic grade difluoroethylene carbonate, greatly reduces the generation amount of hazardous wastes, reduces the environmental protection cost, has simple process and low energy consumption, and is suitable for large-scale production and application.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Under the protection of nitrogen, adding 348g of high-activity anhydrous potassium fluoride and 560ml of dimethyl carbonate dehydrated by a molecular sieve into a 3000ml four-neck flask, connecting devices such as a condenser vent pipe and the like, starting stirring, starting heating, raising the temperature to 70 ℃, dropwise adding 400g of dichloroethylene carbonate (with the purity of 98%) by using a constant-pressure dropping funnel, dropwise adding for 2 hours, after finishing dropwise adding, carrying out heat preservation reaction for 1 hour, cooling, filtering, and washing the flask and filter residues by using 140ml of dimethyl carbonate to obtain 1kg of filtrate. Transferring the obtained filtrate to a distillation device, distilling and recovering the solvent at normal pressure, recovering the solvent to obtain 510g of dimethyl carbonate, continuing to distill the rest filtrate at reduced pressure, and obtaining 320.9g of difluoroethylene carbonate with the GC content of 87.62 percent after the distillation is finished. Further rectifying and purifying to obtain 290g of high-purity difluoroethylene carbonate with the GC content of 97.65 percent. Crystallization sweating purification is adopted to obtain difluoroethylene carbonate with higher purity, and 278g of difluoroethylene carbonate with high purity, 99.99 percent of GC content and 89.78 percent of yield can be obtained through multiple times of crystallization sweating.
Example 2
Under the protection of nitrogen, adding 348g of high-activity anhydrous potassium fluoride and 560ml of dimethyl carbonate dehydrated by a molecular sieve into a 3000ml four-neck flask, connecting devices such as a condenser vent pipe and the like, starting stirring, starting heating, raising the temperature to 80 ℃, dropwise adding 400g of dichloroethylene carbonate (with the purity of 98%) by using a constant-pressure dropping funnel, wherein the dropwise adding time is 2 hours, after finishing dropwise adding, carrying out heat preservation reaction for 1 hour, cooling and filtering, and washing the flask and filter residues by using 140ml of dimethyl carbonate to obtain 1kg of filtrate. Transferring the obtained filtrate to a distillation device, distilling and recovering the solvent at normal pressure, recovering the solvent to obtain 490g of dimethyl carbonate, continuing distilling the rest filtrate at reduced pressure, and obtaining 302g of difluoroethylene carbonate with the GC content of 85.43 percent after the distillation is finished. Further rectification and purification are carried out to obtain 273g of high-purity difluoroethylene carbonate with the GC content of 97.52%. Crystallization sweating purification is adopted to obtain high-purity difluoroethylene carbonate, and 245g of high-purity difluoroethylene carbonate with the GC content of 99.99 percent and the yield of 79.13 percent can be obtained through repeated crystallization sweating.
Example 3
Under the protection of nitrogen, 580g of high-activity anhydrous potassium fluoride and 850ml of dimethyl carbonate dehydrated by a molecular sieve are added into a 3000ml four-neck flask, devices such as a condenser vent pipe and the like are connected, stirring is started, heating is started, the temperature is increased to 70 ℃, 400g of dichloroethylene carbonate (with the purity of 98%) is dropwise added by a constant-pressure dropping funnel for 2 hours, after dropwise addition is finished, heat preservation reaction is carried out for 1 hour, the temperature is reduced, filtration is carried out, the flask and filter residues are washed by 200ml of dimethyl carbonate, and 1.4kg of filtrate is obtained. Transferring the obtained filtrate to a distillation device, distilling and recovering the solvent at normal pressure, recovering the solvent to obtain 720g of dimethyl carbonate, continuing distilling the rest filtrate at reduced pressure, and obtaining 285g of difluoroethylene carbonate with the GC content of 86.45 percent after the distillation is finished. Further rectifying and purifying to obtain 270g of high-purity difluoroethylene carbonate with the GC content of 97.89%. Crystallization sweating purification is adopted to obtain high-purity difluoroethylene carbonate, and 253g of high-purity difluoroethylene carbonate can be obtained through multiple crystallization sweating, the GC content is 99.99 percent, and the yield is 81.71 percent.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. A preparation method of difluoroethylene carbonate is characterized by comprising the following steps: the method comprises the following steps:
s1: adding a certain amount of solid fluoride into a container at room temperature under the protection of nitrogen, adding a solvent, and stirring and mixing uniformly;
s2: dropwise adding ethylene dichlorocarbonate into an S1 mixed system for reaction at a certain temperature, after dropwise adding is finished for 2-6 hours, monitoring the reaction by using a gas chromatography after dropwise adding is finished, and cooling and finishing the reaction when the content of the ethylene dichlorocarbonate is lower than 0.1%;
s3: filtering out solid insoluble substances after the reaction of S2 is finished, and carrying out reduced pressure rectification on the mother liquor to obtain a crude product;
s4: purifying the difluoroethylene carbonate to electronic grade through continuous crystallization and sweating;
s5: the solvent was recovered during the rectification in S3.
2. The method for preparing difluoroethylene carbonate according to claim 1, wherein: the solvent in step S1 includes, but is not limited to, one or more of ethyl acetate, methyl acetate, ethyl propionate, γ -butyrolactone, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate, and most preferably, dimethyl carbonate is used.
3. The method according to claim 1, wherein the solvent used in step S1 is a solvent
And (4) solvent after molecular sieve dehydration.
4. The method for preparing difluoroethylene carbonate according to claim 1, wherein: in the step S1, the fluoride is one or more of sodium fluoride, potassium fluoride, triethylamine trihydrofluoride and fluorinated quaternary ammonium salt, and most preferably, potassium fluoride is selected.
5. The method for preparing difluoroethylene carbonate according to claim 1, wherein: the reaction temperature in the step S2 is 50-100 ℃.
6. The method for preparing difluoroethylene carbonate according to claim 1, wherein: in the step S2, the purity of the dichloroethylene carbonate is 80-98%, and the equivalent ratio of the dichloroethylene carbonate to the potassium fluoride is 1: 1-1: 5.
7. The method for preparing difluoroethylene carbonate according to claim 1, wherein: and the reaction time after the dropwise addition in the step S2 is 1-2 hours.
8. The method for preparing difluoroethylene carbonate according to claim 1, wherein: the operation temperature of the vacuum rectification in the step S3 is 30-110 ℃, and the operation pressure is 20-100 mmHg.
9. The method for preparing difluoroethylene carbonate according to claim 1, wherein: in the step S4, the crystallization sweating temperature-reducing speed is maintained at 1-10 ℃/h, and the temperature-increasing speed is maintained at 1-10 ℃/h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115611846A (en) * | 2022-11-10 | 2023-01-17 | 广州理文科技有限公司 | Preparation method of high-purity ethylene carbonate fluoro derivative |
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2021
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115611846A (en) * | 2022-11-10 | 2023-01-17 | 广州理文科技有限公司 | Preparation method of high-purity ethylene carbonate fluoro derivative |
| WO2023179071A1 (en) * | 2022-11-10 | 2023-09-28 | 广州理文科技有限公司 | Method for preparing high-purity fluorination derivative of ethylene carbonate |
| CN115611846B (en) * | 2022-11-10 | 2024-07-09 | 广州理文科技有限公司 | Preparation method of high-purity fluoroderivatives of ethylene carbonate |
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Application publication date: 20220208 |